Production of polymeric oil



July 26, 1949.

Filed Nov. 9, 1945 GRH/V1.5

D. E. BADERTSCHER ETAL 2,477,538

PRoDUcTloN oF POLYMERIC oIL 4 Sheets-Sheet I so E AGENT 0R ATT NEY July 26, 1949. D. E. BADERTSCHER ETAL 2,477,538

PRODUCTION OF POLYMERIC OIL Filed Nov. 9, 1945 4 Sheets-Sheet 2 July 26, 1949. D.. E. BADERTscHER ErAL 2,477,533

PRODUCTION 0F POLYMERIC OIL Filed Nov. 9, 1945 4 Sheets-Sheet 3 0 25 o 75 loo 25 5 0 TIF/WHA rz//PE 06.r

HYDRUGEA/ FL l/OR/DE 20 grams T/P/axyMfTH n ENE Hymn.; :so TEM/fwwf -25 C.

AGENTUR A /RNEY July 26, 1949.

Filed Nov D. E. BADERTSCHER ETAL PRODUCTION OF POLYMERIC OIL 4 Sheets-Sheet 4 AGENT 0R ATT Patentedl July'` 26, 1949 UNITED STATES PATENT oFFlcE PRODUCTION OF POLYMERIC OIL Y Darwin E. Badertscher, Woodbury, and Richard B. Bishop, Haddonfield. N. J., assignors to Soi" cony-Vacuum Oil Company, Incorporated, a corporation of New York Application November 9, 1945, Serial No. 627,758

Claims.

This invention relates to the production of viscous oils suitable for use as plasticizers for various resins such as the vinyl .esins, softeners for synthetic rubbers, fluids for hydraulic systems, uids for quartz testing and the like. A

The present application is a continuation-inpart of our application Serial No. 463,938, filed October 30, 1942, now Patent No. 2,397,398, wherein there is disclosed a process for producing resinous materials, particularly light-colored resinous materials having relatively high melting points from aromatic hydrocarbon materials such as benzene, toluene, xylenes, mesitylenes, naphthalene, alpha and beta-methyl naphthalenes, polymethyl naphthalenes, anthracene, etc. Preferred as inexpensive aromatic hydrocarbon materials are petroleum fractions rich in aromatic hydrocarbons. Typical, and particularly preferred,l of such aromatic petroleum fractions are those obtained by catalytic cracking or cyclization, or catalytic cracking and cyclization, of petroleum stocks and having boiling ranges from about 300 F. to about 400 F., and from about 500 F. to about 750 F.; and those obtained by thermal cracking of petroleum stocks and having boiling ranges from` about 400 F. to about 600 F.

In general, all aldehydes are contemplated herein for condensation with the foregoing aromatic hydrocarbons in the presence of hydrogen fluoride. Representative aldehydes are formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, toluic aldehydes, etc. `The aliphatic alde- `The amount of hydrogen uoride used may be varied from about 1.5 per cent to about 25 per cent by weight of the reaction mixture but, in general, most satisfactory results are obtained with concentrations of about 5 per cent to about 15 per cent by weightof the reaction mixture. The

` aldehyde may be varied within a wide range and the temperature for batch operation may be beliq- 2 tween -5 centigrade and 95 centigrade. However, in continuous operation employing a heating zone and a zone in which the reaction products are rapidly cooled, temperatures above 100 centigrade and of the order of 400 C. to 1000 C.

l with residence times of the order of two minutes or less may be employed.

The relation of the variables time, temperature and hydrocarbon I: aldehyde hydrogen uoride is established for batch operation in Table I and the drawings Fig. 1 and Fig. 2. These data were obtained in the following manner. The hydrocarbon, trioxymethylene and hydrogen iluoride were placed in a small, cold (0 C.) 500 cubic centimeters bomb (copper lined) which was then immediately capped and placed in a violent reciprocating shaker, where it was maintained at the desired temperature for the desired reaction time. After shaking for the desired period, the bomb was opened and the HFneutralized with 20 per cent potassium hydroxide. The emulsion which usually formed was broken with petrohol and benzene. The layers were then separated and the hydrocarbon layer was passed through a lter bed of Super Filtrol. The filtrate, a clear yellowred colored liquid was then distilled using a side arm flask equipped with a total take-off condenser. That material which boiled above the boiling range of the charge material and below 300 C. at 10 millimeters was defined as oil. The portion remaining in the flask after such a distillation was recorded as resin.

Using this procedure a series of runs were made on each variable. `Studies were made on the effectof (a) concentration of hydrogen fluoride, (b) concentration of trioxymethylene, (c) effect of temperature, and (d) elect `of time. Two stocks ("Sovasol #75 and aromatic petroleum stock boiling range 40G-525 F.) were treated in this` manner. The results of this work are itemized n Table I. Figures 1a, 2a, 3a. and 4a illustrate graphically the` results itemized in Table I employing an aromatic petroleum stock in which `in which the aromatic compounds comprise essentially polynuclear aromatic hydrocarbons,

`such as naphthalene and alkylated naphthalenes.

se 'stock C. the

series or a matee series. the resine has as an essenhich has a basic unit y the Formula III.

the benzene taining hydrocarformaldehyde or resinous oil boil'- imeters of mercuryV a polymer, preted by the formula are small integers not v es over at 10 millimeters tock is either a hydroseries. a mixture ot hyocarbon of s and tic petroleum stock boiling predominant constituents are the anthracen ployed. the ng point of the char C. at 10 mill petroleum stock, boiling range triileum stock boiling range 40G-525' F.-

is dened as resin.

C. ght of aroma l which maybe represented by Formula l1. Bimilarly, when the charge s carbon of the anthracene drocarbons oi' the anthracene rial of which the hydrocarbons of ous oil as deilned hereinbefor tial constituent a polymer w which can be represented b When an aromatic hydr series or a `charge stock con bons of the benzeneserie its polymers are em ine above the bolli and below 300 has as an essential constituent dominantly the dimer represen in which a: and u are alkyl groups having 1 to e carbon atoms and n and m greater than 5.

Aromatic pe after stripp g run at 10 millimeters and 300 remaining material Oil-that product which com between 130-300 Molecular wei range 400-52 Teer.: I

pping run at 10 millimeg material lil deilned as The resinous materials boiling above the boiling range oi' the charge material and below 300 C. at 10 millimeters of mercury have as an essen- Oil intermediates and resin from "Sovasol" and aromatic tial constituent at least one polymer of an aromatic hydrocarbon, which polymer has a unit which may be represented byone or more of the following formulae depending upon the character of the charge stock and 2.4044 2.4 0.9.2.0.... on wuneuwn on annahm au. m m M mmmnnm m mwwmmmmdmm a u ma 0.34.008Bml. 094.144. .N122 ministers meinem. vm m m il w. 5 munsuuum mwsmm ma m m wmmmmm .,mlm .mmmmwwm mm n m m m m n o me.. .mmmmmmmmmmmmwwmmmm mm m .c m t e. m m.. Quang qwnu w n s um ...Oss-usanza 5656-02 20a T m D.. n e n B .M12 .llllllmlna .1111 11 mm M mm mmmsmmmmmmlmmsmmmm mm G e w .Mmmmmu Humanas. om.. .n M m Muunnmuuuu nnnnmnu nu m a r .M 5555.055 5.o um M222222222 LLLLLLW. LL m Mmmwmmmwmw mwmmmmw um G m W n La aens mun n um Remarks "SovasoP #75 resin-after stri teglia and 300 C. the reinainin re n. Oil-that product which comes over at 10 millimeters between -300 C. y olecular weight of "SovasoP #75, 121.

tfoa-bbvzb-m- M-.m.n. mmmmmmm Mmmm m e ememmuemmmmmmmm m wrm@ M ...Hmm ...1M mmmmmoml eine .taimmymmmftn kaf. aanmeten emmmmsmmsmmm am me ,0. t 1 nmmmnmmmmmwmmymmm, mmmmmomamemnmme, e mhwmwmimmmmme www .unmvimna mwa mmm. m wororwmmfmm Woe. cda n 0 e e mmmnmmammmn Mmmm@ mmmmmocmwm meenemen y? me mmmmw .mmlkm .memmwmemhmmn c une@ memwhmbamm mmnmmmamwmmwmwns mmmmmmmmmmmm@ iet.naem.m .n m e mmmwmmmmmummmm .ammmmrmmae m swwnuwmtmmcmtma .mlmwe um ...,.em News.. .mmwhm memm mmmmmmmwwms mwmmmmmmmmmmmmm mmmmmmmmmmwwmemmm i cup) 100 F. were used with 35 grams of trimost as much effectiveness as a molar ratio of 2-1-1. The temperature of the reaction has no appreciable effect between -5 C. and 95 C. However, at higher temperatures short reaction times well below the two hours minimum used in these operations can be used;

The properties of the resinous materials obtained as contemplated by this invention may be modified by varying one or more of a number of influencing factors. Thematerials may be of various degrees of hardness or softness, of brittleness or toughness, and maybe light or dark in color, etc.. depending upon the reaction conditions. Temperature, time, concentration of hydrogen fluoride, ratio of reactants, treatment following resinication (such as distillation) etc., all may be regulated to obtain resinous materials of different properties. The products obtained may be used in paints, var'nishes and lacquers.

in molding compositions, as shellac replacements,

as electrical insulating materials, and waxes or extenders lor more expensive resins such as the polystyrene resins and earn-aube. wax. etc.

As aforesaid, hydrogen fluoride is effective for i the condensation of aromatic hydrocarbons and aldehydes over a wide range of temperatures including both low temperatures and relatively high temperatures. In this respect, hydrogen uoride differs substantially from the related halogen acids,` hydrochloric and hydrobromic acids which are effective ascatalysts Ior their reactions at relatively high temperatures only. To demonstrate this difference in activity, comparative results of the preparationof resinous materials of the type contemplated herein are set forth in Table II below. out in sealedstainless-steel reaction vessels and, in all cases, 250 grams of an aromatic-rich hydrocarbon stock obtained from a catalytic cracking operation of a petroleum stock and identied by the characteristics: boiling range 31o-395 F., Kauri-Butanol No.` 80, ash point (Tag closed oxymethylene and about grams oi anhydrous hydrogen halide. Each reaction was carried out for about 6 hours at either about 25 C. or about 45 180"7 C. as indicated in Table II. With each reaction, the reaction' vessel was opened at the end of about 6 hours and the contents taken up in benzol. The benzol solution was ltered, the

filtrate neutralized with dilute (10 per cent) `50 sodium hydroxide solution and then washed with The preparations were carried V35 6 leaving the resin as the residue. The yield obtainedin each case is given below in Table 1I:

` TABLE II Catalyst- Used (Anhydrous) 'fpj gm;

The results tabulated in Table II clearly indicate that hydrogen iluorlde is eective at both low temperatures (25 C.) and at relatively high temperatures (180 C.) The results also demon-- strate that hydrogen iluoride is a much .more effective condensing agent than either hydrochloric or hydrobromic acids at such temperatures.

To further demonstrate the superiority of hydrogen fluoride over the related halogen acids, hydrochloric and hydrobromic acids, resinous materials were prepared in the presence of the aqueous halogen acids. The preparations were carried out in sealed metal asks maintained at C. In each case, 250 grams of the hydrocarbon used above (Table II) and 35 grams of trioxymethylene were used. The products were treated as described above in discussion of the products shown in Table II. These /rbsults are given in Table III which follows and are selfexplanatory:

TABLE III Catalyst Used Wt. Time Yield (Aqueous) Conc Flask Grains Hrs.' Grams Per cent 48 Copperm. 100 85 38 Steel 100 3 2. 2 48 Copperm. 100 24 The effects of various factors, such as concentration of reactants, temperature, etc., on the yield of resin obtained from an aromatic hydroi TABLE IV Wt of Wt. of Wt. of

Reaction Hydro- Tem Time Yi ld variable om ed cHo I Anh draus P l e g No. um. (Hmm) HF'ygmms C. l hrs. grams 24 250 35 5 100 6 68 a a a 1 6 e W" 0 HF- sa 25o 5o 15 10o s 31 250 i 50 25 100 6 124 32 250 50 35 100 6 140 35 250 25 5 100 6 49 24 250 35 5 100 6 68 34 250 25 15 100 6 56 Wt. of (ECHO): 29 250 35 15 100 6 84 33 250 50 15 100 6 94 22 250 30 25 100 3 81 g gg 100 3 80. 5 0 6 42 Temperatur 26 250 35 25 100 s 74 27 250 35 25 100 3 80. 5 Time 26 250 35 25 100 6 74 28 250 35 25 100 16 B5 wate separated and ltered. The washed benzol filtrate was then distilled to a pot temperature of about 250 C. under about 10 millimeters pressure,

Inspection of the results in Table IV show the following features in connection with the factors susceptible of variation. In general, an increase the other hydrogen halides.

sirable for our purposes.

-arations clearly indicate ananas in the concentration of hydrogen fluoride, other factors remaining constant, appears to increase the yield of resin and an increase in concentration of aidehyde (trioxy-methylene), with other factors the same, also increases the yield of resin; the yield is also aii'ected` by temperature as shown by reactions 20 and 26 above, and by the data in Table II. As aforesaid, however, and asis shown by Table II, yields in commercial quantities of superior resins can be obtained with hydrogen fluoride at low temperatures, for example, C. (reaction 20 above) which is not the case with The period of reaction, atleast within the range of time intervals represented by reactions 26, 27 and 28, does not appear to have any material eifect on the yield.

Reaction 20, of Table IV, demonstrates that hydrogen fluoride is effective at temperatures in the neighborhood of, 0 C. Although the highest reaction temperatures illustrated are at about 180 C., it would appear from the results shown in Tables II and I V that hydrogen fluoride would be effective for the purposes contemplated herein at still higher temperatures, such as, for example, about 200G C.

It will be apparent to those'familiar with the art that glass equipment cannot be used eilectively for the condensation contemplated herein in view of the well-known chemical action of hydrogen fluoride op glass. Equipment made of various metals and alloys of such metals may be used in the preparation of the resinous materials described above. In general, copper, stainless steel and iron reaction vessels are considered most de- As aforesaid, the resinous materials contemplated herein may have different physical properties depending upon the various factors referred to above. The following examples of typical prepresinous materials.` 4

Examen: I

several or' these typical 8 Boiling range:

Initial boiling point F. 504 10% I" 520 F 540 F 660 End point ".F 735 ASTM pour point v F 0 S. U. V. F seconds-- 50 The examples and procedures given hereinabove are intended to be illustrative only, and the inven- A mixture of 250 grams of an aromatic rich hydrocarbon fraction, described above in connection with Table I, 50 grams of trioxymethylene and 35 grams of anhydrous hydrogen fluoride was shaken in a tightly-capped copper flask, in a 100 C. steam bath for 18 hours. The mixture was then cooled, neutralized with 20-25 per cent sodium r hydroxide, taken up in benzene, water washed, filtered and the iiltrate distilled'to a pot temperature of 250 C. under 10 millimeters pressure. The residue, grams, is a light-colored resin with a bali-and-ring melting point of about 89 C.

ExAMrLnII` light-colored resin, 148 grams, with a ball-andring melting l point of about 77 C. was thus obtained.

t ExlunmslII A heavy fuel distillate from a catalytic cracking operation having the following properties:

tion is not to be construed as limited thereto. It IWill be apparent to those skilled in the art that numerous modifications and variations of the illustrative examples and procedures may be ineluded within the scope of the appended` claims.

We claim:

l. A process for producing polymeric oil from petroleum products which comprises reacting an aromatic-rich hydrocarbon fraction having a boiling range of about 310 F. to about 395 F. at atmospheric pressure and obtained by catalytic cracking of a petroleum stock with about 6 to about 27 weight per cent of trioxymethylene based on the weight of the hydrocarbon fraction in the rpresence of about 3 to about 15 weight per cent of hydrogen fluoride based upon the weight of said aromatic-rich fraction at temperatures up to about 1000 C. for a reaction time not greater than about 2 hours for temperatures of minus about 5 C. to plus about 100 C. and for a reaction time not greater than about 2 minutes for temperatures oi' about 400 C. to about 1000 C., cooling `the' `reaction mixture, neutralizing the cooled reaction mixture with aqueous alkali metal hydroxide solution, separating the hydrocarbons from the aqueous solutions, separating insolublematerial from said hydrocarbons and recovering polymeric oil from said separated hydrocarbons as a fraction boiling above about 395@` F. at atmospheric pressure and below about 572 F. at a pressure of 10 millimeters of mercury.

2. A process for producing polymeric oil from petroleum products which comprises reacting an aromatic-rich hydrocarbon fraction havingl a boiling range of about 400 F. to about '600 F.

at atmospheric pressure and obtained by thermal cracking of petroleum stocks with about 6 to about 27 weight per cent of trioxymethylene based upon the weight of the aromatic-richfraction in the presence of about 3 to about l5 weight per cent of hydrogen fluoride based upon the weight of the aromatic-rich fraction at temperatures up to abit 1000 C. for a reaction time not greater than about 2 hours for temperatures of minus about 5 C. to plus about 100 C. and for a reaction time not greater than about 2 minutes for temperatures of about 400 C. to about 1000 C., cooling'the reaction mixture, neutralizing the reaction mixture with aqueous alkali metal hydroxide, separating hydrocarbons from aqueous solution, separating liquid hydrocarbons from insoluble material and recovering kpolymeric oil as a fraction of said liquid hydrocarbons boiling above about 600 F. at atmospheric pressure and below about 572 F. at a pressure of 10 millimeters of mercury.

3. A process for producing polymeric oil from petroleum products which comprises reacting an aromatic-rich hydrocarbon fraction having a boiling range f about 400 F. to about 525 F. at atmospheric pressure and a,l Saybolt Universal Viscosity at 100 F. of about 50 seconds and obtained from a catalytic cracking operation with about 6 to about 27 weight per cent of trioxymethylene based upon the weight of said aromatic-rich fraction in the presence of about 3 to about 15 weight per cent of hydrogen fluoride based upon the Weight of said aromatic-rich fraction at temperatures up to 1000 C. for a reaction time not greater than about 2 hours for temperatures of about minus 5 C. to about 100 C. and for a reaction time not greater than about 2 minutes for temperatures of about 400 C. to about 1000 C., cooling the reaction mixture, neutralizing the reaction mixture with aqueous alkali metal hydroxide, separating hydrocarbons from aqueous solution, separating liquid hydrocarbons from insoluble material and recovering polymeric oil as a fraction of said liquid hydrocarbons boiling above about 735 F. at atmos pheric pressure and below about 572 F. at a pressure of millimeters of mercury.

4. Aprocess for producing polymeric oil from petroleum products which comprises reacting an aromatic-rich hydrocarbon fraction having a, boiling range within the limits about 300 F. to about 750 F. at atmospheric pressure and obtained by cracking petroleum stock with about 6 to about 27 weight per cent of formaldehyde based upon the weight of said aromatic-rich fraction in the presence of about 3 to about 15 weight per cent of hydrogen uoride based upon the Weight of said aromatic-rich fraction at temperatures up to 1000 C. for a reaction time not greater than about 2 hours for temperatures of about minus 5 C. to about 100 C. and for a reaction time not greater than 2 minutes for temperatures of about 400 C. to about 1000 C., cooling the reaction mixture, neutralizing the reaction mixture, separating hydrocarbons from the reaction mixture, separating liquid hydrocarbons from insoluble material, and recovering polymeric `oil as a fraction of said liquid hydrocarbons said fraction of liquid hydrocarbons having an initial boiling point higher than the nal boiling point of the aforesaid aromatic-rich fraction and a nal boiling point below about 572 F. at a pressure of 10 millimeters of mercury.

5. A process for producing polymeric oil from petroleum products which comprises reacting an aromatic-rich hydrocarbon fraction having a boiling range Within the limits about 3007 F, to about 750 F. at atmospheric pressure and obtained by cracking petroleum stock with about 6 to about 27 weight per cent of formaldehyde based upon the weight of said aromatic-rich fraction in the presence of about 3 to about l5 weight per cent of hydrogen fluoride based upon the Weight of said aromatic-rich fraction, the reaction time being not greater than 2 hours for temperatures of about minus 5 C. to about 100 C., and not greater than 2 minutes for temperatures of about 400 C. to about 1000 C., cooling the reaction mixture, neutralizing the reaction mixture, separating hydrocarbons from the reaction mixture, separating liquid hydrocarbons from insoluble material, and recovering polymeric oil as a fraction of said liquid hydrocarbons, said fraction of liquid hydrocarbons having an initial boiling point higher than the final boiling point of the aforesaid aromatic-rich fraction and a nal boiling point below about 572 F. at a pressure of 10 millimeters of mercury.

DARWIN E. BADERTSCHER. RICHARD B. BISHOP.

REFERENCES CITED The following references are of record inthe le of this patent:

UNITED STATES PATENTS Number Name Date 2,237,634 Rosen Apr. 8, 1941 2,275,312 Tinker et al Mar. 3, 1942 2,397,398 Badertscher et al. Mar. 26, 1946 FOREIGN PATENTS Number `Country Date 403,264 Germany Aug. 9, 1919 OTHER REFERENCES Calcott et al.: Journal American Chem. Soc., April 1939, volume 61, pages 949-51.

Fulton et al.: Industrial and Engineering Chemistry, vol. 32, No. 3, March 1940, pages 304- 309.

Simons: Industrial and Engineering Chemistry, vol. 32, 1940, pages 178-180. 

